CN102800553A - Gas/liquid chromatogram-electron bombardment electrospray dual-ion-source flight time mass spectrum system - Google Patents
Gas/liquid chromatogram-electron bombardment electrospray dual-ion-source flight time mass spectrum system Download PDFInfo
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- CN102800553A CN102800553A CN2012103182727A CN201210318272A CN102800553A CN 102800553 A CN102800553 A CN 102800553A CN 2012103182727 A CN2012103182727 A CN 2012103182727A CN 201210318272 A CN201210318272 A CN 201210318272A CN 102800553 A CN102800553 A CN 102800553A
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Abstract
The invention provides a gas/liquid tandem mass spectrum system with a multimode ionization ion source. The gas/liquid tandem mass spectrum system is characterized by being formed by connecting a multimode ionization ion source, a gas chromatography, a Liquid Chromatography, a mass analyzer with purification and enrichment functions, and a flight time mass spectrometry in series. According to the invention, the applicability of a single-ion-source mass spectrometry specific to analysis of polymorphic samples is broadened, meanwhile, the high resolution performance of fragment ions on mass selection and analysis is enhanced, and the researches on an ionic reaction mechanism are realized.
Description
Technical field
The invention belongs to the scientific instrument technical field, be specifically related to a kind of gas phase liquid chromatogram-dual ion source tandem mass spectrum of electron bombard electron spray system.
Background technology
The accurate qualitative function of the separation and quantitative ability that chromatogram is powerful and mass spectrum (MS) combines and the chromatograph-mass spectrometer coupling technology that forms is one of strong technological means of analyzing at present organic molecule content and inorganic elements form branch.In existing chromatograph-mass spectrometer coupling technology; The chromatographic technique that relates to comprises gas-chromatography (GC), liquid chromatogram (LC), thin-layer chromatography (TLC) and chromatography of ions (IC), and the mass-spectrometric technique of coupling then should have quadrupole rod (Q) mass spectrometer, ion trap (IT) mass spectrometer and flight time (TOF) mass spectrometer etc. mutually with it.In chromatogram and mass spectral coupling process, the condition of high vacuum degree specification requirement of interpretation of mass spectra just can be carried out structure elucidation and quantitative analysis after making the gaseous state that flows out from chromatogram or liquid sample need adopt certain way ionization.At present; To flowing phase in the chromatographic technique mainly is the characteristics of gas and liquid; The ionization technique of having developed and having utilized has electron impact ionization (EI) technology, chemi-ionization (CI) technology, electron spray ionisation (ESI) technology and APCI (APCI) technology etc., and there are GC-EI/CI-MS, LC-ESI/APCI-MS, TLC-ESI/APCI-MS and IC-ESI-MS etc. in the chromatograph-mass spectrometer coupling system of formation.
Above-mentioned various multi-form chromatograph-mass spectrometer coupling technology with technical pattern has obtained development fast under field actual demands such as industrial and agricultural production and scientific technological advance promote; Each instrument factory commercial city has been produced dissimilar and chromatograph-mas spectrometer function both at home and abroad; And the intellectual property that has core is technological; Like liquid chromatograph mass spectrography technology US5240616A, GB2151021A, gas chromatography-mass spectrography technology US5837883A, JP8327622A, US5686655A, US5837883A and thin-layer chromatography-mass spectrometric hyphenated technique JP2091559A, JP62209352A; In recent years; Under the demand of rapid screening and portable detection technique, the detection mode of arising at the historic moment includes vehicle-mounted gas chromatography-mass spectrography technology ZL 200920105060.4 and the on-the-spot technology ZL 00807325.2 of gas chromatography-mass spectrography fast and portable gas chromatography-mass spectrometric hyphenated technique US5525799A etc. at the scene.Then; Chromatogram with mass spectrometry in above-mentioned these commercial chromatograph-mass spectrometer coupling technology all is single gas-chromatography, liquid chromatogram or thin-layer chromatography; And with the process of mass spectrometry in; The technological difficulties that overcome mainly concentrate on the interfacing aspect of chromatograph-mass spectrometer coupling, this single chromatograph-mass spectrometer coupling technology, and the high efficiency interface mode that is equipped with various ways is (like EI, ESI; CI and APCI etc.), the highly sensitive context of detection of object demonstrates the incomparable advantage of other technologies in to specific modality sample (like the volatile organic compounds of gaseous state, liquid residues of pesticides etc.).Yet, also just because of the high specific of chromatograph-mass spectrometer coupling technology, limited the gas-chromatography of single-mode-, liquid chromatogram-, analysis when thin-layer chromatography-mass spectrometric hyphenated technique is difficult to be applicable to variform sample (gaseous state, liquid state or solid-state); In addition; When developing to the chromatography-mass spectroscopy technology detecting method of unknown character compound; Need to carry out with gas chromatograph-mass spectrometer (GC-MS) and liquid chromatograph-mass spectrometer simultaneously; This approach not only needs expensive chromatograph-mas spectrometer to guarantee; And each chromatograph-mas spectrometer all has difference to the requirement of sample pre-treatments, correction, data record and the operating system of self performance state, reduced and weakened the advantage of chromatograph-mass spectrometer coupling technology on organic compound trace qualitative and quantitative analysis virtually.
To above-mentioned technical background, exist a kind of that can analyze gaseous sample and liquid sample simultaneously and can realize that electron impact ionization and electron spray ionisation switch and have the demand of the gas phase liquid chromatograph-mass spectrometer that the high-resolution quality selects and resolve each other.
The purpose of this invention is to provide a kind of can be simultaneously and the dual ion source gas phase and liquid phase of the electron bombard electron spray chromatogram tandem mass spectrum system of gas-chromatography and liquid chromatogram coupling; Utilize the dual interface technology of novel dual ion source mass analyzer; With the gas-chromatography of traditional single-mode-/the liquid chromatograph mass spectrography technology integrates; Realized the gas-chromatography tandem mass spectrum function parallelly connected in same set of system and equipment, expanded the versatility of gas phase and liquid phase chromatogram tandem mass spectrum system to gaseous sample and liquid sample with the liquid chromatogram tandem mass spectrum; In addition; Get into mass spectral fragment ion and get into mass spectral fragment ion through electron spray ionisation the reaction of different kinds of ions such as adduction, cracking, rearrangement can take place in the same area through electron impact ionization, make gas phase and liquid phase chromatogram tandem mass spectrum of the present invention system become an innovation in the research of ionic reaction mechanism.
Summary of the invention
The purpose of this invention is to provide a kind ofly can separate simultaneously, the system and method for the gas-chromatography/liquid chromatogram-dual ion source massspectrum of electron bombard electron spray of qualitative and quantitative gaseous sample and liquid sample, can only analyze the limitation that gasification sample and liquid chromatogram-(series connection) mass spectrum can only analyzing liquid samples with gas-chromatography-(series connection) mass spectrum of breaking through present commercialization.On vertical interactive time-of-flight mass spectrometer; Be processed with electron impact ion source and perpendicular electric spray ion source simultaneously; Be connected to the method on the electric spray ion source through gas-chromatography being connected to electron impact ion source and liquid chromatogram; Be implemented in the function that to carry out gas-chromatography-time of flight mass analysis on the chromatography-mass spectroscopy analyzer separately or carry out liquid chromatogram-time of flight mass analysis separately or carry out gas-chromatography-liquid chromatogram-time of flight mass analysis simultaneously, only use the purpose of a chromatography-mass spectroscopy analyzer with regard to ability Accurate Analysis gaseous sample and liquid sample thereby reach.
To achieve these goals; The technical scheme that the present invention taked is: a kind of gas phase liquid chromatogram-dual ion source time-of-flight mass spectrometer of electron bombard electron spray and application process thereof is made up of gas chromatograph, liquid chromatograph, the dual ion source time-of-flight mass spectrometer of electron bombard electron spray; Described gas chromatograph is connected with electron impact ion source through the capillary heating muff (107) that is positioned at the dual ion source time-of-flight mass spectrometer of electron bombard electron spray side; Described liquid chromatograph is connected through liquid line (308) with the electric spray ion source that is positioned at the dual ion source flight mass spectrometer of electron bombard electron spray front; The dual ion source time-of-flight mass spectrometer of described gas chromatograph, liquid chromatograph and electron bombard electron spray is connected with hub (401) through data wire (402) respectively; Said hub (401) is connected with control terminal (403).
Described gas chromatograph comprises sample disc (101), auto injection pin (102), column oven (103), quartz capillary column (104), carrier gas steel cylinder (106) and necessary carrier gas and circuit coupling assembling; Gas chromatograph is arranged in the dead ahead of the dual ion source time-of-flight mass spectrometer of electron bombard electron spray electron bombard sample introduction awl (236), and wherein a wherein end of quartz capillary column (104) passes perforate (105) back that is arranged in column oven (103) side and is placed in capillary heating muff (107) and is connected with the electron impact ionization source.
Described liquid chromatograph comprises liquid storage bottle (301), degasser (302), automatic sampler (303), on-line mixing device (304), hydraulic pump (305), chromatographic column (306), six-way valve (307) and necessary liquid line and ionization coupling assembling; Parallel left side or the right side that is arranged in the dual ion source time-of-flight mass spectrometer of electron bombard electron spray spray chamber (202) of liquid chromatograph; Wherein liquid storage bottle (301) is connected through liquid line (308) front and back successively with degasser (302), hydraulic pump (305), on-line mixing device (304), chromatographic column (306); Automatic sampler (303) also is connected through liquid line (308) front and back successively with on-line mixing device (304), chromatographic column (306), six-way valve (307), and the liquid line (308) of drawing from six-way valve is connected with electron spray nozzle needle (201).
The dual ion source time-of-flight mass spectrometer of described electron bombard electron spray is combined by electron impact ion source, electric spray ion source and two-way vertical introduction-type time of flight mass analyzer; The gaseous sample that flows into electron impact ion source from quartz capillary column (104) is positioned on the Z axle through the electron bombard ion beam passage front end that forms after the ionization; Flow into the electron spray ion beam passage front end that the liquid sample of electric spray ion source forms from liquid line (308) and be positioned on the X axle after spraying ionization, the electron bombard ion beam is positioned on the Y axle with the ion accelerated passage that the electron spray ion beam gets into vertical introduction-type time of flight mass analyzer; Described electron impact ion source directly is connected with vertical introduction-type time of flight mass analyzer through electric set of lenses (211); Described electric spray ion source through ion transfer system and vertical introduction-type time of flight mass analyzer anteroposterior diameter to being connected.
Described electron impact ion source comprises anode (237), filament (238), repeller electrode (239), bombardment ionization chamber (240), electric set of lenses (241) and necessary circuit coupling assembling; Electron impact ion source is built in the mass spectrum vacuum chamber (207), is guaranteed the necessary condition of high vacuum degree of operate as normal of its related accessory by prime mechanical pump and molecule turbine pump (235) equal vacuum accessory.
Described electric spray ion source comprises electron spray nozzle needle (201), electric spray sample introduction awl (203), spray chamber (202) and necessary circuit and gas path device; Wherein electron spray nozzle needle (201) passes spray chamber (202) and is positioned at the top of spray chamber (202); Electron spray nozzle needle (201) is the 60-90 degree with the angle of electron spray Stainless Steel Capillary conduit (204), and whole electric spray ion source is operated under the standard atmospheric pressure environment.
Described vertical introduction-type time of flight mass analyzer comprises accelerating region (221), field-free flight district (222), echo area (227), detection zone (233) and supporting circuit arrangement, and the function of its high-resolution mass resolution is realized by two accelerating regions and Shuan Chang echo area; Described two accelerating regions comprise accelerating region repeller plate (215), quicken aperture plate (216), accelerating region aperture plate (220) and accelerating region pole piece (218); Described Shuan Chang echo area comprises first order reflection aperture plate (223), secondary reflex aperture plate (225), reflecting plate (226) and echo area pole piece (224).
Described ion transfer system is made up of the triple quadrupole bar in order, comprises first group of quadrupole rod (208), second group of quadrupole rod (210) and a component daughter ion reactor (209).Ion through first group of quadrupole rod (208) separates after selecting is accomplished crash response in molecular ion reactor (209); After second group of quadrupole rod (210) and electric set of lenses (211) modulation, pass electron spray ion beam entrance slit (212) and get in the mass analyzer again.
The application process of described gas phase liquid chromatogram-dual ion source time-of-flight mass spectrometer of electron bombard electron spray; It is characterized in that instrument is automaticallying switch between gas-chromatography-electron bombard-flight time pattern, liquid chromatogram-electron spray-flight time pattern, gas phase liquid chromatogram-electron bombard electron spray-three kinds of mode of operations of flight time pattern: when starting gas-chromatography-electron bombard-flight time pattern; Inject the injection port promoting the circulation of qiization of going forward side by side behind the sample in auto injection pin (102) the draw samples dish (101); Adsorb/separate after the gasification sample gets into quartz capillary column (104) with carrier gas; Sample after the separation flows into directly ionization in bombardment ionization chamber (240) behind the electron bombardment ionization source successively; The ion that ionization produces moves along Z-direction, after electric set of lenses (211) modulation, forms electron bombard ion beam current (243) form with ion packet under the high-voltage pulse repulsion of accelerating region repeller plate (215) and gets into time of flight mass analyzer accelerating region (221) along the Y direction; When launching liquid chromatogram-electron spray-flight time pattern; The liquid sample that automatic sampler (303) extracts gets into on-line mixing device (304) with flowing phase under the pump function of hydraulic pump (305); After chromatographic column (306) is separated, flow through six-way valve (307) and get into electron spray nozzle needle (201) of the sample that mixes along liquid line (308); The high-tension current that loads on electron spray nozzle needle (201) syringe needle place is ionized into ion with liquid sample; Introduce in the mass spectrum vacuum chamber (207) through electron spray Stainless Steel Capillary conduit (204); Pass electron spray sampling spiroid (205) back and get into the ion transfer system; The electron spray ion beam current (242) that after modulation, forms penetrates along directions X, and likewise the form with ion packet gets into time of flight mass analyzer accelerating region (221) along the Y direction under the high-voltage pulse repulsion of accelerating region repeller plate (215); When starting gas phase liquid chromatogram-electron bombard electron spray-flight time pattern; The parallel draw samples of automatic sampler (303) in auto injection pin (102) in the gas chromatograph and the liquid chromatograph, the sample that gets into quartz capillary column (104) and chromatographic column (306) flows into electron impact ion source and electric spray ion source after separating.The electron bombard ion beam current (243) that their ionization produces gets into vertical the crossing of time of flight mass analyzer accelerating region (221) along the Z direction with directions X respectively with electron spray ion beam current (242); Mixed ion is pushed in the time of flight mass analyzer accelerating region (221) along the Y direction with the form of ion packet by high pressure repulsion pulse and quickens, and gets into field-free flight district (222), echo area (227) and detection zone (233) again and carries out qualitative and detection by quantitative.
The application process of described gas phase liquid chromatogram-dual ion source time-of-flight mass spectrometer of electron bombard electron spray; It is characterized in that the automatic switchover of described chromatography-mass spectroscopy mode of operation; After any one pattern in having selected gas-chromatography-electron bombard-flight time pattern, liquid chromatogram-electron spray-flight time pattern, gas and liquid phase chromatographic apparatus-electron bombard electron spray-three kinds of mode of operations of flight time pattern; Chromatograph and mass spectrometric interlock circuit, stream and gas circuit will be adjusted within the desired working range of this mode of operation under software systems control automatically, provide condition indicative signal after the to be switched completion.
Characteristics of the present invention are through gas chromatograph, liquid chromatograph and the triplicity of the dual ion source time-of-flight mass spectrometer of electron bombard electron spray have been realized the dual ion source time-of-flight mass spectrometer of gas phase liquid chromatogram-electron bombard electron spray; Complete machine can automatically switch between gas-chromatography-electron bombard-flight time pattern, liquid chromatogram-electron spray-flight time pattern, gas phase liquid chromatogram-electron bombard electron spray-three kinds of mode of operations of flight time pattern; Be implemented in the function of accomplishing gas phase chromatography-flying time mass spectrum analysis and liquid chromatogram-flying time mass spectrum analysis on the instrument respectively or simultaneously; Can improve the dual ion source time-of-flight mass spectrometer of gas phase liquid chromatogram-electron bombard electron spray and be directed against the function that same sample is realized different analytical models, can improve the applicability of complete machine again the different qualities sample analysis.
Description of drawings
Fig. 1 is the system organization figure of gas phase liquid chromatogram-dual ion source time-of-flight mass spectrometer of electron bombard electron spray.
Vertical view when Fig. 2 carries out gas-chromatography-electron bombard-flight time mode state for complete machine.
Front view when Fig. 3 carries out liquid chromatogram-electron spray-flight time mode state for complete machine.
Fig. 4 is the fundamental diagram of time of flight mass analyzer.
Fig. 5 is the mass spectrogram that whole machine using gas-chromatography-electron bombard-flight time pattern analysis sulfamerazine obtains.
Fig. 6 is total ion current figure, selection ion flow graph and the mass spectrogram that whole machine using liquid chromatogram-electron spray-flight time pattern analysis pyrrole worm nitrile obtains.
In the accompanying drawing: 101. sample disc; 102. auto injection pin; 103. column oven; 104. quartz capillary column; 105. perforate; 106. carrier gas steel cylinder; 107. capillary heating muff; 201. electron spray nozzle needle; 202. spray chamber; 203. electric spray sample introduction awl; 204. electron spray Stainless Steel Capillary conduit; 205. electron spray sampling spiroid; 206. vacuum pumping port; 207. mass spectrum vacuum chamber; 208. first group of quadrupole rod; 209. molecular ion reactor; 210. second group of quadrupole rod; 211. electric set of lenses; 212. electron spray ion beam entrance slit; 213. accelerating region radome electron spray ion beam entrance slit; 214. accelerating region radome electron bombard ion beam entrance slit; 215. accelerating region repeller plate; 216. quicken to delete net; 217. accelerating region radome electron spray ion beam exit slit; 218. accelerating region pole piece; 219. accelerating region radome; 220. accelerating region aperture plate; 221. accelerating region; 222. field-free flight district; 223. net is deleted in first order reflection; 224. echo area pole piece; 225. net is deleted in secondary reflex; 226. reflecting plate; 227. echo area; 228. detection zone is deleted net; 229. detection zone radome; 230. microchannel plate; 231. integrated micro-channels plate detector; 232. to time-to-digit converter; 233. detection zone; 234. vacuum gauge; 235. molecule turbine pump; 236. electron bombard sample introduction awl; 237. anode; 238. filament; 239. repeller electrode; 240. bombardment ionization chamber; 241. electric set of lenses; 242. electron spray ion beam current; 243. electron bombard ion beam current; 244. accelerating region incident electron spray ion beam projection; 245. accelerating region incident electron bombarding ion bundle projection; 246. detection zone outgoing electron spray ion beam projection; 247. detection zone outgoing electron bombarding ion bundle projection; 301. liquid storage bottle; 302. degasser; 303. automatic sampler; 304. on-line mixing device; 305. hydraulic pump; 306. chromatographic column; 307. six-way valve; 308. liquid line; 401. hub; 402. data wire; 403. control terminal; 405. printer.
Embodiment
Shown in accompanying drawing 1; Gas phase liquid chromatogram of the present invention-dual ion source time-of-flight mass spectrometer of electron bombard electron spray mainly is made up of the dual ion source time-of-flight mass spectrometer of gas chromatograph, liquid chromatograph and electron bombard electron spray; Wherein gas chromatograph is connected with dual ion source time-of-flight mass spectrometer with built-in electron impact ion source through the capillary heating muff, and liquid chromatograph is connected with dual ion source time-of-flight mass spectrometer with the electric spray ion source of external through liquid phase pipeline.The dual ion source time-of-flight mass spectrometer of gas chromatograph, liquid chromatograph and electron bombard electron spray is controlled by control board respectively; And is connected with hub through data wire, send the instruction operational order of execution different mode afterwards by the control terminal that is connected to hub; Fig. 2 and Fig. 3 have showed the organization chart that the dual ion source time-of-flight mass spectrometer of gas phase liquid chromatogram-electron bombard electron spray carries out gas-chromatography-electron bombard-flight time pattern analysis and liquid chromatogram-electron spray-flight time pattern analysis respectively, and Fig. 4 has then illustrated the core work principle of time of flight mass analyzer.
The side of gas chromatograph column oven (103) faces electron impact ion source; And be provided with a perforate (105) and therefrom pass, and the quartz capillary column (104) that protection is heated extends to electron impact ion source inside to make things convenient for capillary heating muff (107).Gas chromatograph is formed during by sample disc (101), auto injection pin (102), column oven (103), carrier gas steel cylinder (106) and necessary circuit and gas circuit.Electron impact ion source is positioned at the inside of mass spectrum vacuum chamber (207); Face the accelerating region repeller plate (215) of time of flight mass analyzer; Be made up of anode (237), filament (238), repeller electrode (239), bombardment ionization chamber (240), electric set of lenses (241), quartz capillary column (104) and necessary circuit coupling assembling, the necessary condition of high vacuum degree of the operate as normal of its related accessory is guaranteed by prime mechanical pump that is connected to vacuum pumping port (206) and molecule turbine pump (235) equal vacuum accessory.Be injected in the injection port behind the sample of extraction certain volume in the sample bottle that auto injection pin (102) is placed from sample disc (101); Liquid sample is through getting into quartz capillary column (104) under the carrying of carrier gas behind the high-temperature gasification; Gaseous sample after the separating electron impact ion source of flowing through successively; The ion that ionization generates forms the electron bombard ion beam current (243) that penetrates along the Z direction after through the modulation of electric set of lenses (241), and ion beam current passes the electron bombard ion beam entrance slit (214) that is positioned on the accelerating region radome and entering time of flight mass analyzer accelerating region (221).In a repulsion pulse period, the projection (245) of incident electron bombarding ion bundle on accelerating region repeller plate (215) is approximate rectangular.
Flowing phase that hydraulic pump (305) will extract from liquid storage bottle (301) and the sample that extracts from automatic sampler (303) pump into on-line mixing device (304) in the lump; Fully get in the chromatographic column (306) behind the mixing and separate, select control flows to flow into electric spray ion source along liquid line (308) backward through six-way valve (307).The electric spray ion source of being made up of electron spray nozzle needle (201), electric spray sample introduction awl (203), spray chamber (202) and necessary circuit and gas path device is positioned at the outside of mass spectrum vacuum chamber (207); Spray chamber (202) then is positioned at the front end dead ahead of mass spectrum vacuum chamber (207), and whole electric spray ion source is operated under the standard atmospheric pressure environment.Liquid sample is introduced in the mass spectrum vacuum chamber (207) through the electron spray Stainless Steel Capillary conduit (204) that is 60-90 degree angle with nozzle needle at ion that the ionization of electron spray nozzle needle (201) needle point place generates, goes to dissolve the back via electron spray sampling spiroid (205) and gets into the ion transfer system that is made up of the triple quadrupole bar; The electron spray ion separates selection back entering molecular ion reactor (209) by first group of quadrupole rod (208) and carries out crash response in the ion transfer system; Be modulated into electron spray ion beam current (242) through second group of quadrupole rod (210) and electric set of lenses (211) again, pass electron spray ion beam entrance slit (212) and accelerating region radome electron spray ion beam entrance slit (213) and enter in the repulsion district of time of flight mass analyzer accelerating region (221).In a repulsion pulse period, the projection (244) of incident electron spray ion beam on accelerating region repeller plate (215) is approximate rectangular, and with incident electron bombarding ion bundle projection (245) square crossing.
The vertical ion of introducing time of flight mass analyzer accelerating region (221); The electron bombard ion beam current (243) or their hybrid ionic that have comprised the electron spray ion beam current (242) injected from directions X, injected from the Z direction; Ion is quickened by repulsion along the Y direction immediately, and electron spray ion beam current (242) incident direction, electron bombard ion beam current (243) incident direction and this three of time of flight mass analyzer acceleration direction have formed configuration perpendicular to each other thus.Ion passes through accelerating region (221), field-free flight district (222), echo area (227) and detection zone (233) successively; Their movement locus in the time of flight mass analyzer are parabola shaped, and the ion channel of electron spray ion beam current (242) and electron bombard ion beam current (243) overlaps at this.Detection zone (233) at the time of flight mass analyzer; The ion signal that microchannel plate (230) is collected transfers to time-to-digit converter (232) behind integrated micro-channels plate detector (231) record, finally be delivered to control terminal (403) through data wire (402) through hub (401) after converting digital signal into.
Embodiment 1 gas-chromatography-electron bombard-flight time mode of operation.
Like Fig. 2 and shown in Figure 4; After control terminal (403) sends instruction; Auto injection pin (102) is sought according to instruction and is injected injection port after sample disc (101) goes up the sample bottle of appointment and extracts the sample solution of certain volume; The high-pure helium air-flow that sample is provided by the back retinue's carrier gas steel cylinder (106) that gasifies gets into quartz capillary column (104) and adsorbs/separate; Sample after the separation gets into helium flow in the bombardment ionization chamber (240) of electron impact ion source successively, and the vacuum degree of bombarding ionization chamber (240) this moment is issued to 10 at the prime mechanical pump of vacuum-evacuate (206) connection and the acting in conjunction of molecule turbine pump (235)
-4Below the pa; The voltage that loads on the filament (238) excites filament (238) to launch the electronics that energy is 70 eV, electronic beam current in the way of flying to anode (237) with vertical direction on sample molecule bump and make it to fragment into the electrically charged fragment of different mass-to-charge ratioes; Charged fragment ion is modulated into electron bombard ion beam current (243) through electric set of lenses (241) under the effect of repeller electrode (239); Pass the electron bombard ion beam entrance slit (214) that is positioned on the accelerating region radome and get into time of flight mass analyzer accelerating region (221), in the time of flight mass analyzer, carry out accurate qualitative and quantitative analysis subsequently.
This moment, electric spray ion source and ion transfer system all quit work, and were ready.
Embodiment 2 liquid chromatograies-electron spray-flight time mode of operation.
Like Fig. 3 and shown in Figure 4; Sample after control terminal (403) sends and instructs in automatic sampler (303) the draw samples bottle; After getting into on-line mixing device (304) in the lump in company with flowing phase under the effect of hydraulic pump (305), mix; Flowing into chromatographic column (306) then adsorbs/separates; Select control flows to inject electron spray nozzle needle (201) along liquid line (308) backward through six-way valve (307), make the drop ionization of outflow in the high voltage electric field at electron spray nozzle needle (201) needle point place; Charged drop rapidly atomizing and desolvation in spray chamber (202), then charged ion is flowed through in electron spray Stainless Steel Capillary conduit (204) the input mass spectrum vacuum chamber (207), and goes to dissolve through electron spray sampling spiroid (205); Triple quadrupole bar ion transfer system has played the effect that radially connects electric spray ion source and vertical introduction-type time of flight mass analyzer, comprises first group of quadrupole rod (208), molecular ion reactor (209) and second group of quadrupole rod (210); Ion after the screening is again after electric set of lenses (211) is modulated into electron spray ion beam current (242); Pass electron spray ion beam entrance slit (212) and accelerating region radome electron spray ion beam entrance slit (213) and enter into time of flight mass analyzer accelerating region (221), in the time of flight mass analyzer, carry out accurate qualitative and quantitative analysis subsequently.
This moment, electron impact ion source quit work, and was ready.
Embodiment 3 gas phases liquid chromatogram-electron bombard electron spray-flight time mode of operation.
Like Fig. 2, Fig. 3 and shown in Figure 4; Auto injection pin (102) sample in draw samples dish (101) carries out in gas-chromatography-electron bombard-flight time pattern analysis, carries out the analysis of liquid chromatogram-electron spray-flight time pattern in the sample input chromatographic column (306) in automatic sampler (303) the draw samples bottle.In bombardment ionization chamber (240) internal ionization, liquid sample is then according to electron spray nozzle needle (201) the needle point place ionization of the approach shown in the embodiment 2 at electric spray ion source according to the approaches and methods shown in the embodiment 1 for gaseous sample in the quartz capillary column; Under the vertical accelerating region repeller plate (215) of electron spray ion beam current (242) of introducing of directions X, cross from the vertical electron bombard ion beam current of introducing (243) of Z direction and through electric set of lenses (211) through electric set of lenses (241), mix the back and quickened by repulsion along the Y direction at time of flight mass analyzer accelerating region (221); No matter be instance 1 with instance 2 in single ionic or this instance in hybrid ionic; Their movement locus all roughly overlaps: pass through accelerating region (221), field-free flight district (222), echo area (227) and detection zone (233) successively, the mass motion track is parabola shaped; The ion signal that microchannel plate (230) is collected transfers to time-to-digit converter (232) behind integrated micro-channels plate detector (231) record, finally be delivered to control terminal (403) through data wire (402) through hub (401) after converting digital signal into.
Gas-chromatography-the electron bombard of embodiment 4 sulfamerazines-flight time pattern analysis.
With residue of veterinary drug sulfamerazine (Sulfamethazine, C
12H
14N
4O
2S, molecular weight: 278.33) be representative species, utilize after being dissolved in it in acetonitrile gas-chromatography-electron bombard-flight time pattern to carry out the qualitative and quantitative calibration.Concrete steps are following: the sulfamerazine that accurately takes by weighing 0.025 g places the brown volumetric flask of 50 mL, adds other acetonitrile of chromatographically pure level to scale, is configured to the standard inventory solution of 500 μ g/mL; The standard liquid shifting equipment of utilization accurately pipettes the standard inventory solution of 10 μ L, transfers in the brown tool plug centrifuge tube of 10 mL, adds trifluoroacetic acid aqueous solution then to scale, and being mixed with concentration is the standard operation solution of 0.5 μ g/mL.Pipette standard operation solution to the sample bottle rear seal-cover of about 1.5 mL and place on the sample disc.After the amount of drawing of setting auto injection pin is 1 μ L; After treating that the operating state of flight time mass spectrum is ready; Start the beginning analysis instruction; This moment, complete machine carried out qualitative analysis according to the mode of operation of embodiment 1 to sulfamerazine, and it is as shown in Figure 5 finally to be delivered to the analysis result of control terminal by time-to-digit converter.
Liquid chromatogram-electron bombard-flight time the pattern analysis of embodiment 5 residues of pesticides pyrrole worm nitriles.
With residues of pesticides pyrrole worm nitrile (molecular weight: 436.9660) be representative species, utilize after being dissolved in it in methyl alcohol liquid chromatogram-electron spray-flight time pattern to carry out the qualitative and quantitative calibration.Concrete steps are following: the pyrrole worm nitrile that accurately takes by weighing 0.025 g places the brown volumetric flask of 50 mL, adds other methyl alcohol of chromatographically pure level to scale, is configured to the standard inventory solution of 500 μ g/mL; The standard liquid shifting equipment of utilization accurately pipettes the standard inventory solution of 10 μ L, transfers in the brown tool plug centrifuge tube of 10 mL, adds chromatographically pure methyl alcohol then to scale, and being mixed with concentration is the standard operation solution of 0.5 μ g/mL.Pipette standard operation solution to the sample bottle rear seal-cover of about 1.5 mL and place on the automatic sampler.After the amount of drawing of setting automatic sampler through control terminal is 5 μ L; After treating that the operating state of flight time mass spectrum is ready; Start the beginning analysis instruction; This moment, complete machine carried out qualitative analysis according to the mode of operation of embodiment 2 to pyrrole worm nitrile, and it is as shown in Figure 6 finally to be delivered to the analysis result of control terminal by time-to-digit converter.
Claims (7)
1. the dual ion source time-of-flight mass spectrometer of gas phase liquid chromatogram-electron bombard electron spray comprises gas chromatograph, liquid chromatograph, the dual ion source time-of-flight mass spectrometer of electron bombard electron spray; Described gas chromatograph is connected with electron impact ion source through the capillary heating muff (107) that is positioned at the dual ion source time-of-flight mass spectrometer of electron bombard electron spray side; Described liquid chromatograph is connected through liquid line (308) with the electric spray ion source that is positioned at the dual ion source flight mass spectrometer of electron bombard electron spray front; The dual ion source time-of-flight mass spectrometer of described gas chromatograph, liquid chromatograph and electron bombard electron spray is connected with hub (401) through data wire (402) respectively; Said hub (401) is connected with control terminal (403); The dual ion source time-of-flight mass spectrometer of described electron bombard electron spray is combined by electron impact ion source, electric spray ion source and two-way vertical introduction-type time of flight mass analyzer; The gaseous sample that flows into electron impact ion source from quartz capillary column (104) is positioned on the Z axle through the electron bombard ion beam passage front end that forms after the ionization; Flow into the electron spray ion beam passage front end that the liquid sample of electric spray ion source forms from liquid line (308) and be positioned on the X axle after spraying ionization, the electron bombard ion beam is positioned on the Y axle with the ion accelerated passage that the electron spray ion beam gets into vertical introduction-type time of flight mass analyzer; Described electron impact ion source directly is connected with vertical introduction-type time of flight mass analyzer through electric set of lenses (211); Described electric spray ion source through ion transfer system and vertical introduction-type time of flight mass analyzer anteroposterior diameter to being connected.
2. the gas phase liquid chromatogram according to claim 1-dual ion source time-of-flight mass spectrometer of electron bombard electron spray; It is characterized in that: described gas chromatograph comprises sample disc (101), auto injection pin (102), column oven (103), quartz capillary column (104), carrier gas steel cylinder (106) and necessary carrier gas and circuit coupling assembling; Gas chromatograph is arranged in the dead ahead of the dual ion source time-of-flight mass spectrometer of electron bombard electron spray electron bombard sample introduction awl (236), and wherein a wherein end of quartz capillary column (104) passes perforate (105) back that is arranged in column oven (103) side and is placed in capillary heating muff (107) and is connected with the electron impact ionization source.
3. the gas phase liquid chromatogram according to claim 1-dual ion source time-of-flight mass spectrometer of electron bombard electron spray; It is characterized in that: described liquid chromatograph comprises liquid storage bottle (301), degasser (302), automatic sampler (303), on-line mixing device (304), hydraulic pump (305), chromatographic column (306), six-way valve (307) and necessary liquid line and ionization coupling assembling; Parallel left side or the right side that is arranged in the dual ion source time-of-flight mass spectrometer of electron bombard electron spray spray chamber (202) of liquid chromatograph; Wherein liquid storage bottle (301) is connected through liquid line (308) front and back successively with degasser (302), hydraulic pump (305), on-line mixing device (304), chromatographic column (306); Automatic sampler (303) also is connected through liquid line (308) front and back successively with on-line mixing device (304), chromatographic column (306), six-way valve (307), and the liquid line (308) of drawing from six-way valve is connected with electron spray nozzle needle (201).
4. the gas phase liquid chromatogram according to claim 1-dual ion source time-of-flight mass spectrometer of electron bombard electron spray; It is characterized in that: described electron impact ion source comprises anode (237), filament (238), repeller electrode (239), bombardment ionization chamber (240), electric set of lenses (241) and necessary circuit coupling assembling; Electron impact ion source is built in the mass spectrum vacuum chamber (207), is guaranteed the necessary condition of high vacuum degree of operate as normal of its related accessory by prime mechanical pump and molecule turbine pump (235) equal vacuum accessory.
5. the gas phase liquid chromatogram according to claim 1-dual ion source time-of-flight mass spectrometer of electron bombard electron spray; It is characterized in that: described electric spray ion source comprises electron spray nozzle needle (201), electric spray sample introduction awl (203), spray chamber (202) and necessary circuit and gas path device; Wherein electron spray nozzle needle (201) passes spray chamber (202) and is positioned at the top of spray chamber (202); Electron spray nozzle needle (201) is the 60-90 degree with the angle of electron spray Stainless Steel Capillary conduit (204), and whole electric spray ion source is worked under the standard atmospheric pressure environment.
6. the gas phase liquid chromatogram according to claim 1-dual ion source time-of-flight mass spectrometer of electron bombard electron spray; It is characterized in that: described vertical introduction-type time of flight mass analyzer comprises accelerating region (221), field-free flight district (222), echo area (227), detection zone (233) and supporting circuit arrangement, and the function of its high-resolution mass resolution is realized by two accelerating regions and Shuan Chang echo area; Described two accelerating regions comprise accelerating region repeller plate (215), quicken aperture plate (216), accelerating region aperture plate (220) and accelerating region pole piece (218); Described Shuan Chang echo area comprises first order reflection aperture plate (223), secondary reflex aperture plate (225), reflecting plate (226) and echo area pole piece (224).
7. the gas phase liquid chromatogram according to claim 1-dual ion source time-of-flight mass spectrometer of electron bombard electron spray; It is characterized in that: described ion transfer system is made up of the triple quadrupole bar in order, comprises first group of quadrupole rod (208), second group of quadrupole rod (210) and a component daughter ion reactor (209); Ion through first group of quadrupole rod (208) separates after selecting is accomplished crash response in molecular ion reactor (209); After second group of quadrupole rod (210) and electric set of lenses (211) modulation, pass electron spray ion beam entrance slit (212) and get in the mass analyzer again.
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